CN115006606A - Hydrophilic lubricating coating and preparation method and application thereof - Google Patents
Hydrophilic lubricating coating and preparation method and application thereof Download PDFInfo
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- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
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- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
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Abstract
The invention provides a hydrophilic lubricating coating and a preparation method and application thereof, belonging to the technical field of material surface modification. The hydrophilic lubricating coating provided by the invention consists of two layers: comprises a cross-linking polymer adhesion active layer at the bottom and a polymer-polyelectrolyte brush composite layer at the surface. The interface adhesion strength of the coating and the base material reaches 1.5MPa, the mechanical modulus reaches 10MPa, the water resistance is strong, and the coating can keep long-term adhesion stability in media such as deionized water, buffer solution, normal saline and the like; the coating has better bearing performance, and the surface friction coefficient under high load can be as low as 0.02. The modification preparation method is simple, the substrate universality is strong, and the prepared coating has excellent stability and lubricating property and is expected to be widely applied in the fields of surface engineering and biomedical devices.
Description
Technical Field
The invention relates to the technical field of material surface modification, in particular to a hydrophilic lubricating coating and a preparation method and application thereof.
Background
For an interventional medical device (e.g., a medical catheter), in order to successfully reach a lesion site for diagnosis and treatment, it should have the following characteristics: the surface has excellent lubricating property, otherwise, the surface can scratch the human body; has good biocompatibility and avoids secondary damage such as inflammation and the like.
At present, two methods for improving the water lubricating performance of the interventional catheter are mainly used: one method is to coat the outer wall of the conventional body conduit with a lubricating fluid. For example, US 5620738A discloses a technique for coating a hydrophilic lubricating coating of modified polyvinylpyrrolidone (PVP) on the surface of a body catheter, and although the modified catheter has good lubricity, the PVP coating and a base material are often cross-linked through non-chemical bonds, so that the PVP is easily peeled off after water absorption and expansion, and the hydrophilic lubricating effect on the surface of the catheter is lost.
Disclosure of Invention
The invention aims to provide a hydrophilic lubricating coating, and a preparation method and application thereof. The interface of the hydrophilic lubricating coating prepared by the invention.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a hydrophilic lubricating coating, which comprises the following steps:
mixing a hydrophilic acrylic-based monomer, a hydrophobic alkyl ester monomer, an adhesive monomer, a bromine-containing initiator monomer, an initiator and a reaction medium for free radical polymerization reaction to obtain an adhesive copolymer; the adhesive monomer is dopamine methacrylamide;
mixing the adhesive copolymer, a curing cross-linking agent and a solvent medium for curing to obtain a cross-linked polymer adhesive active layer;
under a protective atmosphere, immersing the cross-linked polymer adhesion active layer into an atom transfer radical polymerization reaction solution for polymerization reaction to form a polymer-polyelectrolyte brush composite layer, and obtaining the hydrophilic lubricating coating; the atom transfer radical polymerization reaction solution comprises a reaction solvent, a reaction monomer, 2-bipyridine and cuprous bromide.
Preferably, the mass ratio of the hydrophilic acrylic-based monomer, the adhesive monomer, and the hydrophobic alkyl ester monomer is 1:1:10 to 1:4: 25.
Preferably, the bromine-containing initiator monomer is used in an amount of 1 to 5% by mass based on the total mass of the hydrophilic acrylic-based monomer, the adhesive monomer, and the hydrophobic alkyl ester monomer.
Preferably, the hydrophilic acrylic-based monomer includes one or more of acrylic acid, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate.
Preferably, the hydrophobic alkyl ester monomer comprises one or more of ethyl methoxyacrylate, propyl methoxyacrylate, butyl methoxyacrylate, methyl methoxyacrylate, ethyl ethoxyacrylate, propyl ethoxyacrylate and butyl ethoxyacrylate.
Preferably, the structural formula of the bromine-containing initiator monomer is shown as formula I:
in the formula I, R is methyl or hydrogen, and n is 1, 2 or 3.
Preferably, the curing crosslinking agent is 1, 6-hexamethylene diisocyanate, diphenylmethane diisocyanate or toluene diisocyanate.
Preferably, the reactive monomer comprises one or more of 3-sulfopropyl methacrylate potassium salt, sulfobetaine methacrylate, methacryloyloxyethyl trimethyl ammonium chloride, sodium methacrylate, hydroxyethyl methacrylate and 2-methacryloyloxyethyl phosphatidylcholine.
The invention also provides the hydrophilic lubricating coating prepared by the preparation method in the technical scheme, which is characterized by comprising a cross-linking type polymer adhesion active layer and a polymer-polyelectrolyte brush composite layer.
The invention also provides the application of the hydrophilic lubricating coating in the technical scheme in the fields of surface engineering and biomedical equipment modification.
The invention provides a preparation method of a hydrophilic lubricating coating, which comprises the following steps: mixing a hydrophilic acrylic-based monomer, a hydrophobic alkyl ester monomer, an adhesive monomer, a bromine-containing initiator monomer, an initiator and a reaction medium for free radical polymerization reaction to obtain an adhesive copolymer; the adhesive monomer is dopamine methacrylamide; mixing the adhesive copolymer, a curing crosslinking agent and a solvent medium for curing to obtain a crosslinking type polymer adhesive active layer; immersing the cross-linked polymer adhesion active layer into an Atom Transfer Radical Polymerization (ATRP) reaction solution for polymerization reaction under a protective atmosphere to form a polymer-polyelectrolyte brush composite layer, so as to obtain the hydrophilic lubricating coating; the atom transfer radical polymerization reaction solution comprises a reaction solvent, a reaction monomer, 2-bipyridine and cuprous bromide.
The hydrophilic lubricating coating provided by the invention has excellent interface bonding and anti-swelling stability in an aqueous medium, and has a low friction coefficient under a high load, and the excellent interface bonding and anti-swelling stability depends on the excellent interface bonding capability and anti-medium swelling performance of a cross-linked polymer adhesion active layer on the surface of a base material; the low friction coefficient under high load depends on the excellent hydration characteristics of the surface polymer-polyelectrolyte brush composite layer, which is explained in detail as follows: 1. interface bonding: the catechol functional groups on dopamine molecules in the adhesive monomers can form hydrogen bonds, covalent bonds or metal coordination bonds with different substrate materials, and the hydrophilic acrylic-based monomers containing hydroxyl groups are crosslinked to form a chemical network under the action of a curing crosslinking agent, so that the polymer adhesive active layer is tightly adhered to the substrate under the combined action of the two aspects; 2. anti-swelling: the synthesized adhesive monomer structure contains a large amount of hydrophobic alkyl ester molecules, so that the anti-swelling performance in liquid is better; 3. low friction coefficient: after the hydrophilic polymer brush is grafted on the surface of the adhesion active layer through ATRP reaction, strong interaction exists between the polymer brush and water molecules to form a stable hydration layer, the water molecules in the hydration layer can freely flow, the effect of shearing force can be adapted, and the friction coefficient is reduced.
The invention has the following beneficial effects:
(1) the modification method is applicable to almost all substrates and medical appliance surfaces; (2) the prepared hydrophilic lubricating coating has strong binding force with a base material and excellent mechanical property; (3) the hydrophilic lubricating coating has excellent anti-swelling and medium stability; (4) the hydrophilic lubricating coating has low friction and high load bearing characteristics; (5) the preparation method of the hydrophilic lubricating coating is simple and the substrate has strong universality.
The data of the examples show that the adhesion strength between the hydrophilic lubricating coating prepared by the method and the substrate is 1.5MPa, and the mechanical modulus is 10 MPa; the water resistance is strong, and the long-term bonding stability can be kept in deionized water, buffer solution, normal saline and other media; taking polydimethylsiloxane balls as a pair, under the load of 10N, taking deionized water as a lubricant, and setting the surface friction coefficient of the coating to be 0.02; the prepared hydrophilic lubricating coating has excellent stability and lubricating property, and is expected to be widely applied in the fields of surface engineering and biomedical devices.
Drawings
FIG. 1 is a schematic structural diagram of a hydrophilic lubricating coating prepared on the surface of a substrate;
FIG. 2 is a cross-sectional view of a scanning electron microscope for preparing a hydrophilic lubricating coating on the surface of a titanium alloy substrate;
FIG. 3 is a graph showing the adhesion strength test of the hydrophilic lubricating coating prepared on the surface of the titanium alloy substrate and the interface of the titanium alloy substrate;
FIG. 4 is a graph of the friction coefficient test results of a hydrophilic lubricating coating prepared on the surface of a titanium alloy substrate;
FIG. 5 is a graph showing the stability evaluation of the hydrophilic lubricating coating prepared on the surface of the titanium alloy substrate in water, PBS buffer solution and physiological saline;
FIG. 6 is a graph of the results of friction coefficient testing of hydrophilic lubricious coatings prepared on different substrate surfaces;
FIG. 7 is an application demonstration of the modification method on the surfaces of a PVC catheter, an oral airway cannula and a titanium alloy artificial joint head.
Detailed Description
The invention provides a preparation method of a hydrophilic lubricating coating, which comprises the following steps:
mixing a hydrophilic acrylic-based monomer, a hydrophobic alkyl ester monomer, an adhesive monomer, a bromine-containing initiator monomer, an initiator and a reaction medium for free radical polymerization reaction to obtain an adhesive copolymer; the adhesive monomer is dopamine methacrylamide;
mixing the adhesive copolymer, a curing cross-linking agent and a solvent medium for curing to obtain a cross-linked polymer adhesive active layer;
under a protective atmosphere, immersing the cross-linked polymer adhesion active layer into an atom transfer radical polymerization reaction solution for polymerization reaction to form a polymer-polyelectrolyte brush composite layer, and obtaining the hydrophilic lubricating coating; the atom transfer radical polymerization reaction solution comprises a reaction solvent, a reaction monomer, 2-bipyridyl and cuprous bromide.
In the present invention, unless otherwise specified, all the raw materials used are commercially available in the art.
The preparation method comprises the following steps of mixing a hydrophilic acrylic-based monomer, a hydrophobic alkyl ester monomer, an adhesive monomer, a bromine-containing initiator monomer, an initiator and a solvent medium for free radical polymerization reaction to obtain an adhesive copolymer; the adhesive monomer is dopamine methacrylamide.
In the present invention, the mass ratio of the hydrophilic acrylic-based monomer, the adhesive monomer, and the hydrophobic alkyl ester monomer is preferably 1:1:10 to 1:4: 25.
In the present invention, the bromine-containing initiator monomer is preferably used in an amount of 1 to 5%, more preferably 2 to 4%, based on the total mass of the hydrophilic acrylic-based monomer, the adhesive monomer and the hydrophobic alkyl ester monomer.
In the present invention, the hydrophilic acrylic-based monomer preferably includes one or more of acrylic acid, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate.
In the present invention, the hydrophobic alkyl ester monomer preferably includes one or more of ethyl methoxyacrylate, propyl methoxyacrylate, butyl methoxyacrylate, methyl methoxyacrylate, ethyl ethoxyacrylate, propyl ethoxyacrylate, and butyl ethoxyacrylate.
In the present invention, the structural formula of the bromine-containing initiator monomer is preferably as shown in formula I:
in the formula I, R is methyl or hydrogen, and n is 1, 2 or 3.
In the present invention, the bromine-containing initiator monomer is preferably prepared by a method comprising the steps of:
mixing a hydroxy methacrylate monomer, triethylamine and dichloromethane, dropwise adding bromoisobutyryl bromide, and filtering, washing and rotary steaming reaction liquid obtained after reaction at the temperature of 0 ℃ in an ice bath and under the nitrogen protection atmosphere to obtain the bromine-containing initiator monomer.
In the present invention, the hydroxy methacrylate monomer is preferably hydroxy ethyl methacrylate, hydroxy propyl methacrylate or hydroxy butyl methacrylate.
In the invention, the molar ratio of the hydroxy methacrylate monomer, the triethylamine and the bromoisobutyryl bromide is preferably 2:1: 2-2.5.
In the present invention, the reaction time is preferably 4 hours.
The present invention is not particularly limited in terms of the specific manner of filtration, washing and rotary evaporation treatment, and may be implemented in a manner known to those skilled in the art.
In the present invention, the washing is preferably performed using methylene chloride.
After the washing is finished, the obtained filtrate is preferably washed for 2 times by using saturated sodium carbonate and saturated sodium chloride solutions respectively in sequence until the pH value of the solution reaches 7.
In the present invention, the initiator is preferably azobisisobutyronitrile, and the amount of the initiator is preferably 0.005 to 2%, more preferably 0.01 to 1%, and even more preferably 0.01 to 0.05% of the total molar amount of the hydrophilic acrylic-based monomer, the adhesive monomer, and the hydrophobic alkyl ester monomer.
In the present invention, the reaction medium is preferably N, N-dimethylformamide, and the amount of the reaction medium used in the present invention is not particularly limited as long as the monomers can be sufficiently mixed.
The order of addition of the hydrophilic acrylic-based monomer, the adhesive monomer, the hydrophobic alkyl ester monomer, the initiator, the bromine-containing initiator monomer and the solvent medium is not particularly limited in the present invention.
In the invention, the temperature of the free radical polymerization reaction is preferably 50-80 ℃, more preferably 70-80 ℃, and the time is preferably 12-24 hours, and more preferably 15-21 hours. In the present invention, the radical polymerization reaction is preferably carried out under a protective atmosphere; the protective atmosphere is preferably nitrogen.
After the free radical polymerization reaction is finished, preferably, dissolving the obtained free radical polymerization reaction product by using ethyl acetate, then settling by using n-hexane, and removing the supernatant; and drying the sediment to obtain the adhesive copolymer.
In the present invention, the time for the n-hexane to settle is preferably 24 hours.
In the present invention, the drying temperature is preferably 60 ℃ and the time is preferably 24 hours. In the present invention, the drying is preferably performed in a vacuum drying oven.
After the adhesive copolymer is obtained, the adhesive copolymer, the curing crosslinking agent and the solvent medium are mixed and cured to obtain the crosslinking type polymer adhesive active layer.
In the present invention, the curing crosslinking agent is preferably 1, 6-hexamethylene diisocyanate, diphenylmethane diisocyanate or toluene diisocyanate.
In the present invention, the amount of the curing crosslinking agent is preferably 10 to 60% by mass of the hydrophilic acrylic monomer.
In the present invention, the solvent medium is preferably dichloromethane, and the amount of the solvent medium used in the present invention is not particularly limited as long as the polymer can be dissolved.
In the invention, the curing temperature is preferably 20-60 ℃, more preferably 30-40 ℃, and the time is preferably 24-96 hours.
The invention mixes the adhesive copolymer, solvent medium and curing cross-linking agent, then coats the mixture on the surface of material and apparatus, and carries out curing to form the cross-linking type polymer adhesive active layer on the surface of material and apparatus.
After the cross-linking type polymer adhesion active layer is obtained, the cross-linking type polymer adhesion active layer is immersed into an atom transfer radical polymerization reaction solution for polymerization reaction under a protective atmosphere to form a polymer-polyelectrolyte brush composite layer, and the hydrophilic lubricating coating is obtained; the atom transfer radical polymerization reaction solution comprises a reaction solvent, a reaction monomer, 2-bipyridine and cuprous bromide.
In the present invention, the protective atmosphere is preferably nitrogen or argon.
In the present invention, the reactive monomer is preferably one or more of 3-sulfopropyl methacrylate potassium salt, sulfobetaine methacrylate, methacryloyloxyethyl trimethyl ammonium chloride, sodium methacrylate, hydroxyethyl methacrylate and 2-methacryloyloxyethyl phosphatidylcholine.
In the invention, the reaction solvent is preferably a mixture of methanol and water, and the volume ratio of the methanol to the water in the mixture is preferably 1: 1-1: 4, and more preferably 1: 2-1: 3.
In the present invention, the molar ratio of the reactive monomer, 2-bipyridine and cuprous bromide is preferably 1:0.01 to 0.05:0.005 to 0.02, and more preferably 1:0.02 to 0.04:0.01 to 0.015.
In the invention, the polymerization reaction temperature is preferably 20-40 ℃, the time is preferably 5-20 min, and more preferably 8 min; the preparation method of the ATRP reaction solution has no special requirements, and the raw materials are fully and uniformly stirred under the protection of argon.
According to the invention, preferably, under a protective atmosphere, the material with the surface modified with the cross-linked polymer adhesion active layer and the apparatus are immersed in ATRP reaction solution for polymerization reaction to generate a polymer-polyelectrolyte brush composite layer, so as to prepare the double-layer hydrophilic lubricating coating.
The invention also provides the hydrophilic lubricating coating prepared by the preparation method in the technical scheme, which is characterized by comprising a cross-linking type polymer adhesion active layer and a polymer-polyelectrolyte brush composite layer.
FIG. 1 is a schematic structural diagram of a hydrophilic lubricating coating prepared on the surface of a substrate.
The invention also provides the application of the hydrophilic lubricating coating in the technical scheme in the fields of surface engineering and biomedical equipment modification.
The application method of the hydrophilic lubricating coating is not particularly limited, and the hydrophilic lubricating coating can be coated on corresponding materials and apparatuses. In the present invention, the materials and devices preferably include glass, aluminum sheets, titanium sheets, various alloys, polydimethylsiloxane, plastics, ceramics, animal tissue or bone, and implantable interventional biomedical devices preferably including drainage tubes, cannulas, stents or implant replacements.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation of hydrophilic lubricating coating material and coating modification method
(1) Dissolving 10.41g of hydroxyethyl methacrylate and 4.10g of triethylamine in 30mL of dichloromethane, transferring the mixture into a 250mL round-bottom flask after the mixture is completely dissolved, and introducing nitrogen into an ice bath at the temperature of 0 ℃ for 20 min; 23.21g of bromoisobutyryl bromide was dissolved in 10mL of dichloromethane and added dropwise to the round bottom flask using a constant pressure funnel; after stirring and reacting for 4 hours in an ice bath environment at the temperature of 0 ℃, filtering the reaction product to remove white precipitates, and cleaning twice by using dichloromethane; the filtrate was collected and washed 2 times with saturated sodium carbonate and saturated sodium chloride solutions, respectively, until the pH of the solution reached 7. And finally, removing water and residual solvent by rotary evaporation, and collecting light yellow liquid, namely the bromine-containing initiator monomer product.
(2)0.21g of acrylic acid, 0.425g of dopamine methacrylamide, 1.7292g of ethyl methoxyacrylate, 1.08g of butyl ethoxyacrylate, 0.05g of hydroxyethyl methacrylate, 0.07g of a bromine-containing initiator monomer, 0.03g of azobisisobutyronitrile, dissolved in 3ml of N, N-dimethylformamide, N 2 Under protection, reacting at 70 ℃ for 12h, after the reaction is finished, dissolving the obtained product by using 10mL of ethyl acetate, then settling for 24h by using 400mL of n-hexane, removing supernatant, and drying the sediment in a vacuum drying oven at 60 ℃ for 24h to obtain an adhesive copolymer;
(3) the adhesive copolymer was dissolved in 15mL of methylene chloride, and 0.016g of 1, 6-hexamethylene diisocyanate was dissolved in the solution to obtain a mixture; then coating the titanium alloy on a titanium alloy substrate, curing for 24 hours in an oven (40 ℃), and forming a cross-linked polymer adhesion active layer on the surface of the titanium alloy.
(4) 6g of 3-sulfopropyl methacrylate potassium salt, 80mg of 2, 2-bipyridine, 35mg of cuprous bromide, 8mL of deionized water and 4mL of methanol are sequentially added into a 12mL test tube, and the ATRP reaction solution is prepared by fully and uniformly stirring under the protection of argon. And (3) immersing the titanium alloy with the surface modified with the cross-linked polymer adhesion active layer into ATRP reaction liquid, reacting for 8min at room temperature, taking out the titanium alloy after the reaction is finished, and cleaning the titanium alloy with pure water to obtain the hydrophilic lubricating layer grafted with the poly (3-sulfopropyl methacrylate-potassium sulfonate) polyelectrolyte brush.
Example 2
Measurement of appearance, thickness and adhesion strength of hydrophilic lubricating coating and titanium alloy substrate
Measurement of morphology and thickness of hydrophilic lubricating coating: immersing the titanium alloy sheet with the surface modified with the lubricating coating into a PBS (phosphate buffer solution) (pH 7.4) for soaking, putting a sample into a freeze dryer for dehydration after the hydrophilic lubricating layer is swelled and balanced, and then putting the sample into liquid nitrogen for brittle fracture. Scanning electron microscope observation shows that: in example 1, the thickness of the polymer-polyelectrolyte brush composite layer formed on the surface of the cured cross-linked polymer adhesive active layer is 20 μm, the composite lubricating layer and the cross-linked polymer adhesive bottom layer are tightly bonded, and the interface is not separated (fig. 2).
And (3) interface adhesion strength test: the adhesive copolymer prepared in example 1 was uniformly coated between two titanium alloys with an overlapping contact area of 1cm 2 (ii) a After the copolymer is completely cured, a general material tensile tester (EZ-Test, SHIMADZU) is selected to Test the adhesion performance of the coating on the surface of the titanium alloy, a parallel shear Test mode is adopted, and the moving speed of the sensor is 50 mm/min. The results of the experiment are shown in FIG. 3, where the adhesion strength of the copolymer is 1.5MPa, indicating that the bonding between the lubricating coating and the substrate is stable.
Example 3
Mechanical property test of hydrophilic lubricating coating
The hydrophilic lubricating coating prepared in example 1 was used as a Test object, and a general material tensile testing machine (EZ-Test, SHIMADZU) was used to Test the mechanical properties of the coating, and a tensile mode was used, in which the sensor moving speed was 50mm/min, and the tensile modulus of the coating was measured to be 10 MPa.
Example 4
Tribological performance characterization of titanium alloy surface modified with hydrophilic lubricating coating
And (3) adopting a CSM universal friction wear testing machine to represent the water lubricating property of the coating. The lubricant was water, the load was 10N, the friction couple was PDMS balls (radius 6mm), the sliding speed was 1Hz, and the test was performed in 800 cycles. The experimental result is shown in fig. 4, the friction coefficient of the titanium alloy surface modified with the hydrophilic lubricating coating (the cross-linked copolymer active layer + the poly (3-propylmethacrylate-potassium methacrylate) polyelectrolyte brush-copolymer composite layer) is about 0.02; the lubricating coating has good wear resistance, and the water lubricating performance is stable in the 800-cycle test process, which shows that the hydrophilic lubricating coating prepared by the invention has excellent friction reduction and wear resistance.
Example 5
Evaluation of anti-swelling and medium stability of hydrophilic lubricating coating on titanium alloy surface
The titanium alloy substrate with the surface modified with the hydrophilic lubricating coating is respectively immersed in deionized water, PBS buffer solution and physiological saline, and the swelling and structural integrity of the coating are observed. As shown in fig. 5, compared with the sample before soaking (initial state), after soaking in 3 media for 82 days, the lubricating coating has a complete structure, is still tightly bonded with the bonding surface of the substrate, and has no significant swelling phenomenon, which indicates that the hydrophilic lubricating coating prepared by the invention has good anti-swelling and media stability.
Example 6
Modifying hydrophilic lubricating coating on surfaces of various substrates
(1)0.21g of acrylic acid, 0.425g of dopamine methacrylamide, 2.0142g of ethyl methoxyacrylate, 0.78g of butyl ethoxyacrylate, 0.25g of hydroxyethyl methacrylate, 0.08g of a bromine-containing initiator monomer (example 1 is adopted), 0.03g of azobisisobutyronitrile, dissolving in 3mLN, N-dimethylformamide, reacting at 70 ℃ for 12h under the protection of N2, dissolving the obtained product with 10mL of ethyl acetate after the reaction is finished, then settling with 400mL of N-hexane for 24h, removing supernatant, and drying the sediment in a vacuum drying oven at 60 ℃ for 24h to obtain the adhesive copolymer;
(3) dissolving the adhesive copolymer in 15mL of dichloromethane, and dissolving 0.032g of 1, 6-hexamethylene diisocyanate in the solution to obtain a mixture; then coating the polymer on the surface of different types of base materials, and curing for 24 hours in an oven (40 ℃), thus forming a cross-linked polymer adhesion active layer on the surface of the base material.
(4) 4.2g of sulfobetaine methacrylate, 66mg of 2, 2-bipyridine, 30mg of cuprous bromide, 9mL of deionized water and 3mL of methanol were sequentially added into a 12mL test tube, and the mixture was sufficiently and uniformly stirred under the protection of argon to prepare an ATRP reaction solution. And (3) immersing the substrate with the surface modified with the cross-linked polymer adhesion active layer into ATRP reaction liquid, reacting for 15min at room temperature, taking out the substrate after the reaction is finished, and cleaning the substrate with pure water to obtain the hydrophilic lubricating layer grafted with the polysulfonyl betaine methacrylate polyelectrolyte brush.
Example 7
Tribological performance characterization of various substrates with hydrophilic lubricating coatings on their surfaces
And (3) adopting a CSM universal friction wear testing machine to represent the water lubricating property of the coating. The lubricant is water, the load is 10N, the friction couple is PDMS balls (radius 6mm), the sliding speed is 1Hz, and the test is performed in a total cycle of 800 times. The experimental results are shown in fig. 6, the friction coefficients of several substrates are less than 0.04 after the surfaces of the substrates are modified with hydrophilic lubricating coatings (a cross-linked copolymer active layer + a poly sulfobetaine methacrylate polyelectrolyte brush-copolymer composite layer); wherein the surface friction coefficient of the modified Polyethylene (PE) is 0.013, the surface friction coefficient of the modified titanium sheet (Ti) is 0.022, the surface friction coefficient of the modified Polytetrafluoroethylene (PTFE) is 0.023, the surface friction coefficient of the modified steel block is 0.027, the surface friction coefficient of the modified aluminum block (Al) is 0.03, and the surface friction coefficient of the modified copper plate is 0.035; the above experiment results show that the modification method can be used for hydrophilic lubrication modification of the surfaces of different materials.
Example 8
Coating modification verification on medical device surface
(1) Dissolving 12.33g of hydroxybutyl methacrylate and 4.10g of triethylamine in 30mL of dichloromethane, transferring the mixture into a 250mL round-bottom flask after the mixture is completely dissolved, and introducing nitrogen into an ice bath at the temperature of 0 ℃ for 20 min; 23.21g of bromoisobutyryl bromide was dissolved in 10mL of dichloromethane and added dropwise to the round bottom flask using a constant pressure funnel; after stirring and reacting for 4 hours in an ice bath environment at the temperature of 0 ℃, filtering the reaction product to remove a white precipitate, and washing twice by using dichloromethane; the filtrate was collected and washed 2 times with saturated sodium carbonate and saturated sodium chloride solutions, respectively, until the solution pH reached 7. And finally, removing water and residual solvent by rotary evaporation, and collecting light yellow liquid, namely the bromine-containing initiator monomer product.
(2)0.55g of acrylic acid, 1.215g of dopamine methacrylamide, 2.248g of ethyl methoxyacrylate, 3.22g of butyl ethoxyacrylate, 0.15g of hydroxyethyl methacrylate, 0.18g of bromine-containing initiator monomer and 0.08g of azobisisobutyronitrile are dissolved in 10mLN, N-dimethylformamide and reacted at 70 ℃ for 12h under the protection of N2, after the reaction is finished, 35mL of ethyl acetate is used for dissolving the obtained product, 1000mL of N-hexane is used for settling for 24h for three times, the supernatant is removed, and the sediment is dried in a vacuum drying oven at 60 ℃ for 24h to obtain the adhesive copolymer;
(3) dissolving the adhesive copolymer in 15mL of methylene chloride, and dissolving 0.016g of 1, 6-hexamethylene diisocyanate in the solution to obtain a mixture; the PVC catheter, the oral airway cannula and the titanium alloy artificial joint head are respectively selected as instruments to be modified, the adhesive copolymer is coated on the outer surfaces of the instruments in a dip-coating mode, and curing is carried out in an oven (60 ℃) for 12 hours, so that the cross-linked polymer adhesive active layers can be formed on the surfaces of the three medical instruments.
(4) 16g of 2-methacryloyloxyethyl phosphatidylcholine, 220mg of 2, 2-bipyridine, 90mg of cuprous bromide, 20mL of deionized water and 12mL of methanol were sequentially added into a 50mL round-bottom flask, and the mixture was fully and uniformly stirred under the protection of argon to prepare an ATRP reaction solution. Three instruments of which the surfaces are modified with the cross-linked polymer adhesion active layers are immersed into ATRP reaction liquid and react for 10min at room temperature; after the reaction is finished, the instruments are respectively taken out and washed by pure water to obtain the hydrophilic lubricating layer grafted with the poly 2-methacryloyloxyethyl phosphatidylcholine polyelectrolyte brush. As shown in figure 7, the hydrophilic lubricating coating (the cross-linked copolymer active layer + the poly (2-methacryloyloxyethyl phosphatidylcholine) polyelectrolyte brush-copolymer composite layer) can be successfully modified on the surfaces of three medical devices by adopting the method, and the modified coating has uniform appearance, thereby indicating the potential application value of the method in the field of medical devices.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for preparing a hydrophilic lubricating coating, comprising the steps of:
mixing a hydrophilic acrylic-based monomer, a hydrophobic alkyl ester monomer, an adhesive monomer, a bromine-containing initiator monomer, an initiator and a reaction medium for free radical polymerization reaction to obtain an adhesive copolymer; the adhesive monomer is dopamine methacrylamide;
mixing the adhesive copolymer, a curing crosslinking agent and a solvent medium for curing to obtain a crosslinking type polymer adhesive active layer;
under a protective atmosphere, immersing the cross-linked polymer adhesion active layer into an atom transfer radical polymerization reaction solution for polymerization reaction to form a polymer-polyelectrolyte brush composite layer, and obtaining the hydrophilic lubricating coating; the atom transfer radical polymerization reaction solution comprises a reaction solvent, a reaction monomer, 2-bipyridine and cuprous bromide.
2. The method according to claim 1, wherein the mass ratio of the hydrophilic acrylic-based monomer, the adhesive monomer, and the hydrophobic alkyl ester monomer is 1:1:10 to 1:4: 25.
3. The method according to claim 1 or 2, wherein the bromine-containing initiator monomer is used in an amount of 1 to 5% by mass based on the total mass of the hydrophilic acrylic-based monomer, the adhesive monomer and the hydrophobic alkyl ester monomer.
4. The method of claim 1 or 2, wherein the hydrophilic acrylic-based monomer includes one or more of acrylic acid, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate.
5. The method of claim 1 or 2, wherein the hydrophobic alkyl ester monomer comprises one or more of ethyl methoxyacrylate, propyl methoxyacrylate, butyl methoxyacrylate, methyl methoxyacrylate, ethyl ethoxyacrylate, propyl ethoxyacrylate, and butyl ethoxyacrylate.
6. The method of claim 1 or 2, wherein the bromine-containing initiator monomer has a formula represented by formula I:
in the formula I, R is methyl or hydrogen, and n is 1, 2 or 3.
7. The method according to claim 1, wherein the curing crosslinking agent is 1, 6-hexamethylene diisocyanate, diphenylmethane diisocyanate, or toluene diisocyanate.
8. The method of claim 1, wherein the reactive monomer comprises one or more of 3-sulfopropyl methacrylate potassium salt, sulfobetaine methacrylate, methacryloyloxyethyl trimethyl ammonium chloride, sodium methacrylate, hydroxyethyl methacrylate, and 2-methacryloyloxyethyl phosphatidylcholine.
9. The hydrophilic lubricating coating prepared by the preparation method of any one of claims 1 to 8, which is characterized by comprising a cross-linked polymer adhesion active layer and a polymer-polyelectrolyte brush composite layer.
10. Use of the hydrophilic lubricious coating of claim 9 in the fields of surface engineering and biomedical device modification.
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